Water-insoluble styryl dyestuffs containing a pyridyl-lower alkyl group

ABSTRACT

THE PRESENT INVENTION CONCERNS WATER-INSOLUBLE STYRYL DYESTUFFS WHICH ARE CHARACTERIZED BY THE PRESENCE OF A PYRIDYLALKYL GROUP, WHICH IS ATTACHED DIRECTLY OR VIA AN OXYALKYL OR AN AMINOALKYL GROUP TO AN AMINO GROUP WHICH IS IN PARA-POSITION TO THE METHINE GROUP. THESE NEW DYESTUFFS ARE USEFUL FOR DYEING POLYESTER, POLYACRYLONITRILE OR CELLULOSE ACETATE FIBERS FROM AQUEOUS DISPERSION. STRONG GREENISH YELLOW DYEINGS OF EXCELLENT FASTNESS PROPERTIES ARE OBTAINED.

United States Patent 3,804,831 WATER-INSOLUBLE STYRYL DYESTUFFS CON-TAINING A PYRlDYL-LOWER ALKYL GROUP Visvanathan Ramanathan,Klybeckstrasse 18, Basel, Switzerland No Drawing. Continuation ofapplication Ser. No.

872,362, Oct. 29, 1969, which is a continuation-inpart of applicationSer. No. 621,154, Mar. 7, 1967, both now abandoned. This applicationApr. 5, 1972, Ser. No. 241,422

Claims priority, application Switzerland, Mar. 17, 1966,

Int. 01. C091) 23/14 US. Cl. 260-240 R 8 Claims ABSTRACT OF THEDISCLOSURE The present invention concerns water-insoluble styryldyestuffs which are characterized by the presence of a pyridylalkylgroup, which is attached directly or via an oxyalkyl or an aminoalkylgroup to an amino group which is in para-position to the methine group.These new dyestuffs are useful for dyeing polyester, polyacrylonitrileor cellulose acetate fibers from aqueous dispersion. Strong greenishyellow dyeings of excellent fastness properties are obtained.

CROSS REFERENCE TO RELATED APPLICATIONS This application is acontinuation of application Ser. No. 872,362 filed Oct. 29, 1969, nowabandoned, which application was a continuation-impart of applicationSer. No. 621,154 filed Mar. 7, 1967, now abandoned.

The present invention is based on the observation that valuable newwater-insoluble styryl dyestutfs of the for- Y1 in which R is selectedfrom the group of pyridyl-loweralkyl, pyridyl-lower-alkylamino loweralkyl and pyridyllower-alkoxy-lower-alkyl, R is selected from the groupof lower alkyl or lower alkoxy-lower-alkyl which may be substituted byno other groups than hydroxy, cyano, lower alkoxy, aryl, aryloxy,aralkoxy, acyl, acyloxy, or phenyl sulphonyl, X is selected from thegroup of cyano, carboxylic acid ester, lower alkyl-, aralkylor arylsulphonyl and carbonamide and Y and Y each is selected from the group ofhydrogen, chlorine, bromine, lower alkyl and lower alkoxy, and whereinlower means containing at most 4 carbon atoms and acyl means thatradical of a low molecular carboxylic acid containing at most 13 carbonatoms, may be obtained when (a) an aldehyde of the formula in which R RY and Y have the meanings given above, or an aldimine thereof, iscondensed with malonitrile, a cyanoacetic acid ester, lower alkyl-,aralkyl, or arylsulphonylacetonitrile or with a cyanoacetic acid amide,or (b) a styryl derivative of the formula Patented Apr. 16, 1974 'ice inwhich Y and Y have the meanings given above, R is selected from thegroup of lower alkyl, aroyloxy-loweralkyl,arylaminocarbonyloxy-lower-alkyl, lower alkanoyloxy-lower alkyl andbenzyl, and R is selected from the group of hydrogen and lower alkyl.These aldehydes may be obtained by condensing the appropriateN-alkyl-paraaminobenzaldehyde, for example,N-methyl-para-aminobenzaldehyde, N-ethyl-para-aminobenzaldehyde,N-butylpara-aminobenzaldehyde, 2 methyl-4-methylaminobenzaldehyde or2-methyl-4-benzylaminobenzaldehyde, with a vinylpyridine, for example,2-, 3- or 4-vinylpyridineor 2-vinyl-5-methylpyridine.

Condensation between the aldehyde and the malodinitrile or thecyanoacetic acid alkyl ester is advantageously carried out with theapplication of heat in the presence of a basic catalyst, for example,dimethylamine, diethylamine, piperidine, piperidine acetate or sodium orpotassium alcoholate, if desired, in the presence of a solvent, forexample, methanol, ethanol, benzene, toluene, xylene, chloroform orcarbon tetrachloride. When using a solvent, the water formed during thereaction may be removed continuously from the reaction mixture byazeotropic distillation of the slovent, whereby the equilibrium of thereaction is constantly shifted in favor of the condensation product.Condensation may also be carried out in glacial acetic acid or anotherorganic acid acid without the use of a basic catalyst, or in the absenceof a solvent by melting the reactants in the presence of a basiccatalyst, for example, ammonium acetate or piperidine acetate.

The aldehydes may be replaced as starting materials by their aldimines,that is to say, the products obtained by condensing the aldehydes withprimary amines, especially aminobenzenes, in other words, so-calledSchiff bases of the formula in which R preferably represents a benzeneresidue, for example, a phenyl or a sulphophenyl residue. Such aldiminesmay be obtained by condensing the product obtained by reactingformaldehyde and hydrochloric acid with an amine of the formula with anitrobenzene, for example, a nitrobenzene sulphonic acid in the presenceof iron and hydorchloric acid in accordance with Example 17 of UnitedStates patent specification No. 2,583,551.

In method (b) of the process of the invention it is expedient to use asstarting materials compounds of the formula in which 2,, X, Y and Y havethe meanings given above.

Depending on whether Z represents a hydrogen atom or a hydroxyalkylgroup, the reaction with the vinylpyridine is preferably carried out inthe presence of an acid catalyst, for example, glacial acetic acid or inthe presence of a basic catalyst, for example, an alkali metalhydroxide.

After conversion into a finely divided state, the new dyestuffs areeminently suitable for dyeing and printing man-made fibres, for example,fibres made from cellulose diacetate and triacetate, and frompolyacrylonitrile, polyarnides, polyolefines and aromatic polyesters.They produce yellow tints possessing an excellent fastness to light andsublimation.

The following examples illustrate the invention. Unless otherwisestated, the parts and percentages are by weight.

EXAMPLE 1 12.7 parts of 2-(Z-N-methylanilinoethyl)-pyridine are added atto 5 C. to a mixture of 10.5 parts of dimethylformamide and 15.1 partsof phosphorus oxychloride and the batch is heated at about 60 C. for 6hours. After the reaction, the batch is poured on to a mixture of 200parts of ice and 200 parts of Water while stirring well, and the pH isadjusted to 8 to 9 by the addition of sodium hydroxide solution. Aftersome time, the oily aldehyde which precipitates is extracted Withchloroform and the chloroform solution is evaporated.

The aldehyde so obtained is heated to the boil under reflux togetherwith 4.35 parts of malonic acid dinitrile, 0.6 part of piperidine and 60parts of methyl alcohol. The batch turns a deep yellow. After about 4hours the mixture is cooled and poured into 500 parts of water. Thedyestufi of the formula NC CH;

which precipitates is isolated by filtration, washed with water anddried. It dyes polyacrylonitrile and cellulose acetate fibres yellowtints possessing excellent properties of fastness when applied in theform of an aqueous dispersion.

Dyeing prescription 1 part of the dyestulf obtained in the mannerdescribed in this example is ground wet with 2 parts of a 50% aqueoussolution of the sodium salt of 1,1-dinaphthylmethane-2,2'-disulphonicacid.

The dyestufr preparation so obtained is mixed with 40 parts of a aqueoussolutionof the sodium salt of N- benzyl- -heptadecylbenzimidazoledisulphonic acid. A dyebath of 4,000 parts is prepared therefrom bydilution with water. The pH value of the bath is adjusted to 4 to 5 withacetic acid.

100 parts of a cleaned polyacrylonitrile fibre material are entered intothis dyebath at 80 C., the temperature is raised to 100 C. withinminutes and dyeing is carried out for one hour at the boil. Afterdyeing, the bath is slowly cooled to C. and the fibrous material is thenwell rinsed and dried. A strong yellow dyeing possessing excellentproperties of fastness is obtained.

4 EXAMPLE 2 13.56 parts of 3 (Z-N-methylanilinoethyl)-6-methylpyridineare added at 0 to 5 C. to a mixture of 10.5 parts of dimethylformamideand 15.1 parts of phosphorus oxychloride and the batch is heated at 60C. for 6 hours. After the reaction, the batch is poured on to a mixtureof 200 parts of ice and 200 parts of water while stirring well, and thepH is adjusted to 8 to 9 by the addition of sodium hydroxide solution.The oily aldehyde which precipitates is extracted with chloroform andthe chloroform solution is evaporated.

- The aldehyde so obtained is heated to the boil under reflux togetherwth 4.4 parts of malonic acid dinitrile, 0.6 part of piperidine and 60parts of methyl alcohol. The batch turns a deep yellow. After 4 hoursthe mixture is cooled. The dyestutf which precipitates is isolated byfiltration, washed with a small amount of methyl alcohol and dried. Thedyestuff of the formula NC CH3 dyes polyacrylonitrile and celluloseacetate fibres yellow tints possessing excellent properties of fastnesswhen applied in the form of an aqueous dispersion.

EXAMPLE 3 75.5 parts of N(2 hydroxyethyl)-1,3-toluidine, 78.7 parts of2-vinylpyridine and 30 parts of glacial acetic acid are stirred for 40hours at a temperature of about C. The mixture is cooled, a solution of30 parts of sodium hydroxide in 300 parts of alcohol is added and thebatch is boiled for 1 hour under reflux. The alcohol is distilled, theresidue is diluted with chloroform and washed with water until neutral.The chloroform solution is dried and distilled. TheN(2'-hydroxyethyl)-N-2"-2'-pyridylethyl-1, 3-toluidine distils at to C.under a pressure of 0.03 mm. Hg.

12.8 parts of N(2'-hydroxyethyl)-N-2"-2'-pyridylethyl- 1,3-toluidine aredissolved in 35 parts of pyridine. 8.45 parts of benzoyl chloride areadded dropwise at 20 to 25 C., the mixture is heated to 80 C. within 1hour and then stirred for 1 hour. The batch is cooled, poured on to amixture of 200 parts of ice and 200 parts of water, and the pH value isadjusted to 7 by the addition of sodium hydroxide solution. The productis extracted with ether and the ether extract is dried and evaporated.

The benzoyl ester so obtained is added at 0 to 5 C. to a mixture of 8.75parts of dimethylformamide and 12.6 parts of phosphorus oxychloride andthe batch is heated for 6 hours at a temperature pf about 60 C. Afterthe reaction, the batch is poured on to a mixture of 200 parts of iceand 200 parts of water and the pH value is adjusted to 7 to 8 by theaddition of sodium hydroxide solution. The aldehyde which precipitatesis isolated and washed with water and dried.

11.64 parts of the aldehyde so obtained are heated to the boil underreflux together with 2.2 parts of malonic acid dinitrile, 0.3 part ofpiperidine and 30 parts of methyl alcohol. After 4 hours, the mixture iscooled. The dyestutf which precipitates is isolated by filtration,Washed with a small amount of methyl alcohol and dried. The dyestufi? ofthe formula dyes polyester, polyacrylonitrile and cellulose acetatefibres yellow tints possessing excellent properties of fastness whenapplied in the form of an aqueous dispersion.

Dyeing prescription H 1 part of the dyestufli obtained in the mannerdescribed in this example is ground wet with 2 parts of a 50% aqueoussolution of the sodium salt of 1,1-dinaphthylmethane-2,2'-disulphonicacid.

The dyestuff preparation so obtained is mixed with 40 parts of a 10%aqueous solution of the sodium salt of Nbenzyl-u-hepta-decylbenzimidazole disulphonic acid, and then 8 parts ofammonium sulphate are added. A dyebath of 4,000 parts is preparedtherefrom by dilution with water and the pH of the bath is adjusted tobetween 5 and 6 by the addition of formic acid.

100 parts of cleaned polyester fibre material are entered into this bathat 50 C., the temperature is raised to 130 C. within 30 minutes anddyeing is carried out for one hour at that temperature in a closedvessel. The material is then well rinsed. A strong yellow dyeingpossessing excellent properties of fastness is obtained.

EXAMPLE 4 ylethyl-1,3-to1uidine and 7.2 parts of phenylisocyanate areheated for 1 hour at 90 C.

The urethane so obtained is converted into the aldehyde 12.8 parts ofN(2' hydroxyethyl)-N-2",2'-pyridylethand then into the dyestutf by theprocess described in Example 3. The dyestuif of the formula N0 olmo nu-Q/C=HC N\ N0 C211 dyes polyester, polyacrylonitrile and cellulose acetatefibres yellow tints possessing very good properties of fastness whenapplied in the form of an aqueous dispersion.

The following table illustrates a further series of yellow dyestuffs ofthe formula x l R which may be obtained when the correspondingaminobenzaldehyde is condensed with a nitrile of the formula NC-CH --Xby the process described in the preceding examples.

NO. x Y] Y: R: R1

1. C 0 0 C H H C H H 0 Same as above.-

3-..; CONE; H H CH; Do;

4...;. CN B H OH;

Cam-4 \I r H H CH. Same as above.- 5- -7. B 0

0--... CO0CgH H H CH1 Do;

.--.-. C OH H O H I H H CH Same as above 8 .:g S 01 9 COOCIH H H CH: Do.

10..-.- CN B E 0:11

' mmo CsHr- 11...... ON H H 12..... (IN E H 0 11100113 Same as above.-

13....- ON H H 1 H H O ON oammzoam- 15..." ON 00 H CH 16...-. ON 01 1104K. Same as above.-

17....-. ON H OOH. CIHI D0;

is..." c H Do.

ON CsHaOOO-Q-Cl 19...-. ON CH H Do;

ci t c o-@ H.

TABLE'Continued NO. X Y1 Y2 R2 R1 243.-.. O CH; O CH; Same as No. 240.

S0 flHlOCONH OCH:

244.5: Cl OCH; CIHIOCONHCIHO DO.

SO CHa 245.5: CH; C1 OCH: D0.

C 21140 C O NH 246": CH; CaHl 0 CH: CzHtCN D0.

247": CH; CH; 0CH DO.

CaHaC 0 C H C Hg) 248.5: 503GB] H H 03H;

C :HA 0 CaH4 249.5. SOzCH: H CH; CaHg CH5$HCH2OC2H4 N CH; 250...: 802C1H5 H 2 6 C2 5 CH $HCH2NHCHH4 251: SOICIHI OCH; H 04H,

C 1H4]? C 1H CH; N

252-.-- SOzCaH7 OCH: H C H C2H4N-C2Hl 253. SO CH OH H H C H 4CaHuNHCzH4- \Ij 254...- Same as above.-....:.;.-..'.;... H H C4119 CzH4N02114 255...: CH; H CHzCHCHzOCOCHI S O C 11 N C O CH:

256..:: CH: H C1115 S O C 2H40 C2114- I claim: is substituted byhydrogen or lower alkyl, R is lower 1. A water-insoluble styryl dyestutfof the formula in which R is selected from the group ofpyridyl-loweralkyl, pyridyl-lower-alkylarnino lower alkyl andpyridylalkyl or lower alkoxy-lower-alkyl which may be substituted by noother groups than hydroxy, cyano, lower alkoxy, phenyl, toluyl phenoxy,toluyloxy, anisyloxy, benzyl- 70 oxy, acyl, acyloxy, or phenyl sulfonyl,X is selected from the group of cyano, carboxylic acid ester where theester moiety is phenyl, benzyl, toluyl, cyclohexyl, lower alkyl andlower alkyl substituted by lower alkoxy, cyano, benzyl, cyclohexyloxy orpyridyl, lower alkyl sulphonyl,

lower-alkoxy-lower alkyl, and where the pyridyl radical 75 phenyl loweralkyl sulphonyl or phenyl sulphonyl and 29 carbonamide and Y and Y eachis selected from the group of hydrogen, chlorine, bromine, lower alkyland lower alkoxy, and wherein lower means containing at most 4 carbonatoms and acyl means benzoyl, lower alkanoyl, and a group of the formulaor --OCOB where A is phenyl, toluyl, chlorophenyl, methoxyphenyl, loweralkyl or cyclohexyl, and B is lower alkyl, cyclohexyl, chlorophenyl,styryl, benzyl, phenyl, bromophenyl, t-butylphenyl, cyanophenyl, loweralkoxy, phenoxy, and lower alkyl substituted by lower alkoxycarbonyl,phenyl, cyano, lower alkoxy, phenoxy, phenylsulfonyl, and loweralkylcarbonyl.

2. A Water-insoluble styryl dyestutf as claimed in claim 1 of theformula N onion R;

canoQ-r X/ R: Y:

in which R is selected from the group of lower alkyl, benzoyloxylower-alkyl, phenylaminocarbonyloxy-loweralkyl, loweralkanoyloxy-lower-alkyl and benzyl, and R is selected from the group ofhydrogen and lower alkyl.

3. The dyestufi as claimed in claim 1 of the formula NC CH wherein Z isselected from cyano, carbethoxy, phenylsulfonyl and N-loweralkylcarbonamide where the lower alkyl moiety contains p to 4 carbonatoms.

4. The dyestuif as claimed in claim 1 of the formula NC CH;

wherein Z is selected from cyano, carbethoxy, phenylsulfonyl and N-loweralkylcarbonamide where the lower alkyl moiety contains p to 4 carbonatoms.

5. The dyestuflf as claimed in claim 1 of the formula wherein Z isselected from cyano, carbethoxy, phenylsulfonyl and N-loweralkylcarbonamide where the lower alkyl moiety contains up to 4 carbonatoms.

6. The dyestuif as claimed in claim 1 of the formula wherein Z isselected from cyano, carbethoxy, phenylsulfonyl and N-loweralkylcarbonamide where the lower alkyl moiety contains up to 4 carbonatoms.

7. The dyestuif as claimed in claim 1 of the formula wherein Z isselected from cyano, carbethoxy, phenylsulfonyl and N-loweralkylcarbonamide where the lower alkyl moiety contains up to 4 carbonatoms.

8. The dyestuff as claimed in claim 1 of the formula wherein Z isselected from cyano, carbethoxy, phenylsulfonyl and N-loweralkylcarbonamide where the lower alkyl moiety contains up to 4 carbonatoms.

References Cited UNITED STATES PATENTS 260240.9, 294.8 D, 294.8 F, 294.8C, 294.9; 8162 R UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATEOF CORRECTION PATENT NO. 3,804,831 DATED Ap 97 INV ENTOR(S)VISVANA'I'HAN RAMANATHAN It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 1, line 6, insert Assignee: CIBA-GEIGY AG,

Basel, Switzerland Signed and Scaled this Twenty-ninth Day of March 1977[SEAL] Arrest:

RUTH C. MASON C. MARSHALL DANN Arresting Officer Commissioner uj'Parenrsand Trademarks

